Stabilization of aqueous hydroxylamine solutions

ABSTRACT

Solutions of an hydroxylamine or an at least partially neutralized hydroxylamine salt are stabilized against decomposition by adding thereto a mercaptobenzothiazole, a mercaptothiazoline, a thiuram disulfide, thiourea or a mercaptoalkanol.

BACKGROUND OF THE INVENTION

Solutions of hydroxylamine are inherently unstable, decomposing by internal oxidation-reduction to form ammonia and nitrogen or nitrogen oxides. The decomposition is accelerated by high pH and the presence of catalytic amounts of cations such as Fe(II), Ni(II), and Cu(II). Aqueous solutions thereof are commonly produced by at least the partial neutralization of the hydroxylamine salt, such as the hydrochloride or sulfate, with an alkali metal hydroxide or ammonia. These solutions are widely used in synthesis work, but the instability of the free hydroxylamine in these solutions limits its utility in cases where storage is necessary.

There have been a number of attempts reported to stabilize solutions of an hydroxylamine or an at least partially neutralized hydroxylamine salt in order to achieve a longer shelf life. Compounds that have been reported to be stabilizers for such solutions include various chelating agents such as the tetrasodium salt of ethylene diaminetetraacetic acid (U.S. Pat. No. 3,145,082); amide oximes (U.S. Pat. No. 3,480,391); hydroxamic acids (U.S. Pat. No. 3,480,392); hydroxyureas and hydroxythioureas (U.S. Pat. No. 3,544,270); hydroxylalkylidene diphosphonic acids (U.S. Pat. No. 3,647,449); vicinal polyhydroxyphenols (Japanese Patent No. 4,878,099); hydroxyquinolines (Japanese Patent No. 57/100908); 1,10-phenantholine (Japanese Patent No. 58/69841); dipyridyl compounds (Japanese Patent No. 58/69842); thiocarboxylic acids (Japanese Patent No. 58/69843); quinoline derivatives (Japanese Patent No. 58/69844); hydroxy substituted flavone (German Patent No. 33/43597); anthocyanins (U.S. Pat. No. 4,551,318); hydroxyl substituted flavan (German Patent No. 3,343,599); stannic acid (Japanese Patent No. 60/260541); hydroxy substituted anthraquinones (U.S. Pat. No. 4,576,804); 8-hydroxyquinalidines (U.S. Pat. No. 4,629,613); and 2,3-dihydrohexano-1,4-lactone (U.S. Pat. No.4,634,584).

SUMMARY OF THE INVENTION

The present invention provides stabilized solutions of an hydroxylamine or an at least partially neutralized hydroxylamine salt which are stable over a prolonged period, minimizing the decomposition of hydroxylamine. This is achieved by the addition of small amounts of a mercaptothiazole, a mercaptothiazoline, a thiuram disulfide, thiourea or a mercaptoalkanol.

DESCRIPTION OF THE INVENTION INCLUDING PREFERRED EMBODIMENTS

The first class of additives of the present invention include compounds having the formula: ##STR1## wherein R and R¹ are each CHR² groups or R and R¹ together form an aryl or cycloalkyl group, X is hydrogen or a monovalent cation, and each R² is, individually, hydrogen or an alkyl (C₁ -C₄) group.

The 2-mercaptothiazoles useful in the present invention i.e. wherein R and R¹ above, form an aryl or cycloalkyl group are represented by the following formula: ##STR2## where R³ represents a hydrogen atom or a lower hydrocarbon radical, X is as set forth above, and Q is aryl or cycloalkyl. Examples of suitable lower hydrocarbon radicals include C₁ -C₄ alkyl, while such monovalent cations as sodium potassium and ammonium are exemplary.

Exemplary compounds include 2-mercaptobenzothiazole; 2-mercaptocyclohexylthiazole; sodium 2-mercapto-4-methylbenzothiazole; potassium 2-mercapto-6-t-butyl-cyclohexylthiazole etc.

The 2-mercaptothiazolines useful in the present invention, as represented by Formula I, above, are; ##STR3## where R² and X are as set forth above.

Exemplary thiazolines include 2-mercapto-4,5-dimethylthiazoline; sodium 2-mercaptothiazoline; potassium 2-mercapto-5-t-butylthiazoline etc.

The second class of additives of the present invention include compounds having the formula: ##STR4## wherein R⁴, R⁵, R⁶ and R⁷ are, individually, hydrogen, a C₁ -C₁₀ alkyl group or an aryl group, Y is a ##STR5## and n is 0 or 1.

The thiuram disulfides useful in the present invention are those of Formula IV, above, where n is 1, and are represented by the formula: ##STR6## where R⁴, R⁵, R⁶, and R⁷ are as indicated above, most preferably hydrogen. When alkyl, R⁴ -R⁷ are preferably C₁ -C₄ alkyl radicals such as methyl, ethyl, n-butyl, t-butyl etc.

Tetramethylthiuram disulfide; tetra-n-butylthiuram disulfide; N,N'-diethylthiuram disulfide; tetraphenylthiuram disulfide; thiuramdisulfide and the like are representative compounds.

The thioureas of the present invention are those of Formula IV, above, where n is 0, and are represented by the formula: ##STR7## where R⁴ -R⁷ are as indicated above, preferably hydrogen. Examples are thiourea, N,N'-diphenyl thiourea, diortho-tolyl thiourea, ethylene thiourea, and the like.

The third class of additives useful in the present invention are the mercaptoalkanols represented by the formula:

    (HS).sub.a --R.sup.8 --(OH).sub.b                          VII

where R⁸ represents a polyvalent alkylene radical containing 2 to 20 carbon atoms and a and b are integers of 1 to 3, the sum of a and b not exceeding 4. Examples of suitable compounds include 2-mercaptoethanol, 2-mercaptopropanol, 2,11-dimercapto-1,12-dodecanediol, and the like.

The amount of stabilizer to be used to stabilize the hydroxylamine or the at least partially neutralized hydroxylamine salt solution ranges from about 0.001 to about 100 mole %, based on the hydroxylamine salt. Preferably, the amount of stabilizer ranges from about 0.1 to about 10 mole %, same basis. The aqueous solutions of free hydroxylamine i.e. fully neutralized salt, can be produced by the reaction of a salt of hydroxylamine (such as the hydrochloride, the nitrate, the acetate, the sulfate salt etc.) with an alkali metal hydroxide (such as sodium hydroxide) or with ammonia. The concentration of the hydroxylamine or the at least partially neutralized hydroxylamine salt is usually at least about 1 weight percent of the aqueous solution and can range up to saturation or more, but is generally from about 3 to about 30, weight percent. It is best to add the stabilizer to the hydroxylamine salt solution before its neutralization with base, but the stabilizer can also be added to the at least partially hydroxylamine salt solution. The temperature during the stabilizer addition is advantageously kept at from about 5° C. to about 40° C. The stabilized solutions should be stored at temperatures <40° C., preferably <25° C.

The decomposition of the hydroxylamine in aqueous solutions is quite rapid at above pH 7.0 i.e. in the presence of excess base providing immediate evolution of the gaseous by-products. It is convenient to test the ability of a compound to stabilize the hydroxylamine solution by monitoring the amount of gas evolved with time. The stabilized solutions are useful in the preparation of hydroxamated polymers e.g. acrylamide polymers.

The following examples are set forth for purposes of illustration only and are not to be construed as limitations on the present invention except as set forth in the appended claims. All parts and percentages are by weight unless otherwise specified.

EXAMPLE 1 (Comparative)

A suitable reaction vessel is equipped with a thermometer, a pressure equalizing addition funnel, a stirring bar and a gas outlet which is connected to an inverted graduated cylinder filled with water. Into the vessel are charged 39.3 parts (0.144 mole) of 30% aqueous hydroxylamine sulfate solution. While maintaining the temperature below 25° C., 23.0 parts (0.288 mole) of 50% aqueous sodium hydroxide solution are added. The vessel is tightly sealed. Vigorous gas evolution is observed and the water is displaced from the graduated cylinder. 920 Ml of gas are evolved over a period of 4.5 hours. The gas is identified by its infrared absorption spectrum as being mainly nitrous oxide, indictating the decomposition of the hydroxylamine.

EXAMPLE 2

The procedure of Example 1 is repeated except that 1 mole percent of thiourea is added to the hydroxylamine sulfate solution before the addition of the sodium hydroxide. No measurable gas is collected in the cylinder after 16 hours indicating that the hydroxylamine is stabilized.

EXAMPLE 3

Using the same apparatus as in Example 1, 39.3 parts (0.144 mole) of 30% aqueous hydroxylamine sulfate solution are treated with 23.0 parts (0.288 mole) of 50% aqueous sodium hydroxide in the presence of 1 mole % of various stabilizer compounds and the gas evolution is monitored with time. The results are reported in Table I, below.

                  TABLE I                                                          ______________________________________                                         Hydroxylamine Stabilization Studies                                            Gas Collection Over Time                                                       Stabilizer Added     ml Gas  Time (Hr.)                                        ______________________________________                                         None                 880     4.0                                               None                 970     4.5                                               2-Mercaptobenzothiazole                                                                              30     18.2                                              2-Mercaptobenezothiazole                                                                            120     24.3                                              Tetramethylthiuram Disulfide                                                                         80     22.8                                              Tetramethylthiuram Disulfide                                                                         0      45.0                                              8-Quinolinol         500     5.5                                               8-Quinolinol         530     7.8                                               2-Mercaptothiazoline  20     17.7                                              2-Mercaptothiazoline 310     22.5                                              2-Mercaptothiazoline 210     25.0                                              2-Mercaptothiazoline 320     18.5                                              2-Mercaptothiazoline  30     24.5                                              2-Mercaptothiazoline  40     23.4                                              2-Mercaptobenzimidazole                                                                             690     4.7                                               2-Mercaptobenzimidazole                                                                             620     7.0                                               2-Mercaptobenzimidazole                                                                             590     7.0                                               Sodium Diethyl Dithiocarbamate                                                                      600     18.2                                              Thiourea              0      24.0                                              Sodium Diethyl Dithiophosphate                                                                      220     23.0                                              Sodium Diethyl Dithiophosphate                                                                      670     71.0                                              Sodium Diethyl Dithiophosphate                                                                      560     4.0                                               2-Mercaptoethanol    170     23.0                                              Tolylbiguanide       900     7.3                                               Sodium Hydrosulfide  890     6.5                                               Sodium Hypophosphite 850     21.0                                              Sodium Metabisulfite 870     5.0                                               Hydroquinone         690     23.0                                              ______________________________________                                    

EXAMPLES 4-12

Following the procedure of Example 2, various other stabilizers falling within the structural formulae I-VII, above, are employed in lieu of the thiourea. In each instance, gas evolution over 24 hours is reduced significantly when the stabilizer is added as compared to the hydroxylamine solution in the absence of stabilizer. The stabilizers are shown in Table II, below.

                                      TABLE II                                     __________________________________________________________________________     Example                                                                             Formula No.                                                                           Q   R.sup.2                                                                             R.sup.3                                                                            R.sup.4                                                                            R.sup.5                                                                            R.sup.6                                                                            R.sup.7                                                                            R.sup.8                                                                             X  a   b                         __________________________________________________________________________     4    II     benzyl                                                                             --   ethyl                                                                              --  --  --  --  --   K  --  --                        5    II     cyclo-                                                                             --   t-butyl                                                                            --  --  --  --  --   Na --  --                        6    III    hexyl-                                                                             methyl                                                                              --  --  --  --  --  --   NH.sub.4                                                                          --  --                        7    III    --  n-propyl                                                                            --  --  --  --  --  --   K  --  --                        8    V      --  --   --  t-butyl                                                                            t-butyl                                                                            t-butyl                                                                            t-butyl                                                                            --   -- --  --                        9    VI     --  --   --  phenyl                                                                             H   phenyl                                                                             H   --   -- --  --                        10   VI     --  --   --  o-tolyl                                                                            H   o-tolyl                                                                            H   --   -- --                            11   VII    --  --   --  --  --  --  --  propyl                                                                              -- 1(2)                                                                               1                         12   VII    --  --   --  --  --  --  --  dodecyl                                                                             -- 2(2, 11)                                                                           2(1,                      __________________________________________________________________________                                                          12)                   

We claim:
 1. A stabilized solution containing an hydroxylamine or an at least partially neutralized hydroxylamine salt in water and an effective amount of a compound having the formula: ##STR8## wherein R and R¹ are each CHR² groups or together form a substituted or unsubstituted aryl or cylcoalkyl group, X is hydrogen or a monovalent cation and each R² group is, individually, a C₁ -C₄ alkyl group or hydrogen.
 2. The stabilized solution of claim 1 wherein said compound is represented by the formula: ##STR9## where R³ represents a hydrogen atom or a lower hydrocarbon radical, X is as defined therein and Q is aryl or cycloalkyl.
 3. The solution of claim 2 wherein R³ is hydrogen.
 4. The stabilized solution of claim 1 wherein said compound is represented by the formula: ##STR10## where R² and X are as set forth therein.
 5. A process for inhibiting the decomposition of an hydroxylamine or an aqueous solution of at least a partially neutralized hdyroxylamine salt which comprises adding to said solution a stabilizing amount of a compound having the formula: ##STR11## wherein R and R¹ are each CHR² groups or together form a substituted or unsubstituted aryl or cycloalkyl group, X is hydrogen or a monovalent cation and each R² group is a C₁ -C₄ alkyl group or hydrogen.
 6. The process of claim 5 wherein the compound is represented by formula: ##STR12## where R³ represents a hydrogen atom or a lower hydrocarbon radical, X is as defined therein and Q is aryl or cycloalkyl.
 7. The process of claim 6 wherein R³ is hydrogen.
 8. A process according to claim 5 wherein said compound is represented by the formula: ##STR13## where X and R² are as represented therein. 